Catalysts for the Formation of Alcohols from Carbon Monoxide and Hydrogen<sup>1</sup>: I—Decomposition of Methanol by Catalysts Composed of Copper and Zinc

Frolich, Per K.; Fenske, M. R.; Quiggle, D.

doi:10.1021/ie50223a008

“…Carbonyls of iron such as Fe(CO) 5 and Ni(CO) 4 have also been studied as catalyst poisons [210]. These carbonyls can be present in the make-up gases from gasification plants or be generated within the synthesis loop itself from the steel in heat exchangers or in the reactor itself.…”

Section: Other Poisonsmentioning

confidence: 99%

“…Much more active copper-based catalysts were studied and described in the 1920s and 1930s [4][5][6][7][8][9]. These early studies identified copper as a very active metal * Corresponding author.…”

Section: Introductionmentioning

confidence: 99%

Methanol Synthesis

Hansen¹,

Nielsen²

2008

Handbook of Heterogeneous Catalysis

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The sections in this article are Introduction Thermodynamics Methanol Synthesis Catalysts Introduction Zn O / Cr 2 O 3 Catalyst Copper‐Based Catalysts Cu / Zn O + Element ( Al , Cr , … ) Promotion of Cu / Zn O / MOx Catalysts Cu / Zr O 2 Other Cu , Cu / Me , Cu / Me Ox Catalysts Pd ‐Based Catalysts Sulfide Catalysts Other Catalysts Activation of Cu / Zn Catalyst Activity as a Function of the Nature of Copper‐Based Catalysts Catalyst Deactivation Sintering Sulfur Poisoning Other Poisons By‐Product Formation Reaction Mechanism(s) and Active Sites Cu + in a Zn O Matrix as the Active Center The S chottky Junction Theory Partly Oxidized Copper Independent of Support as Active Sites Metallic Copper in Dynamic Interaction with the Support Cu –Zinc Surface Alloy Model Water Gas Shift Reaction Kinetics Reaction Rate Equations Diffusion Restrictions Kinetics in Slurry Phase Methanol Synthesis Methanol Synthesis Technology Synthesis Gas Preparation Natural Gas Reforming Adiabatic Pre‐Reforming Tubular, Fired Reforming Autothermal Reforming and Oxygen‐Fired Secondary Reforming Gasification of Heavy Oil, Coal or Biomass Coproduction in Ammonia Plants and Use of Off‐gases Economics of Synthesis Gas Preparation Reactor Systems and Synthesis Loop Layout Slurry Phase Reactor Types Methanol Purification Concepts Circumventing the Equilibrium Limitations Other Methanol Synthesis Routes and Technologies Methanol Synthesis by Methane Activation Conclusion

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“…CATALYST COMPOSITION MOL Ve The apparatus used in the decomposition and synthesis experiments was identical with that employed in the previous work with zinc and copper catalysts (7). The decomposition apparatus consisted essentially of an electrically heated glass tube through which methanol vapor was passed at a constant rate.…”

Section: Methodsmentioning

confidence: 99%

Catalysts for the Formation of Alcohols from carbon Monoxide and Hydrogen

Cryder¹,

Frolich²

1929

Self Cite

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Experiments on the decomposition of methanol in the presence of catalysts composed of the oxides of zinc and chromium show that an excess of chromium oxide gives rise to reactions producing appreciable amounts of carbon dioxide and unsaturated hydrocarbons. With catalysts containing excess zinc oxide the main products are carbon monoxide and hydrogen, a sharp maximum in activity occurring at a catalyst composition of about Zn7SCr22. The relatively constant percentage of formaldehyde indicates its intermediate formation in the decomposition of methanol.Using the same catalysts for the reverse reaction, it is found that the production of methanol from carbon mon-A PREVIOUS paper from this laboratory (7) dealt with the atmospheric decomposition of methanol by catalysts composed of zinc and copper. The results

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“…Supported copper catalysts have been studied extensively for hydrogen generation from methanol decomposition. For example, CuO/ZnO catalysts are effective for methanol decomposition as well as for the reverse synthesis of methanol from syngas . CuO/ZnO catalysts are active in initial activity tests of methanol decomposition, but their lifetimes are quite short if ZnO is reduced to Zn and then incorporated into the Cu lattice to form Cu‐Zn alloy during the working reaction .…”

Section: Introductionmentioning

confidence: 99%

“…For example, CuO/ZnOc atalysts are effective for methanold ecomposition as well as for the reverses ynthesis of methanol from syngas. [1][2][3][4][5][6] CuO/ZnO catalysts are active in initial activity tests of methanold ecomposition, but their lifetimes are quite short if ZnO is reduced to Zn and then incorporated into the Cu lattice to form Cu-Zn alloy during the working reaction. [7][8][9][10][11] Ba, Mn, or Si added into CuO/ZnOc atalysts improvet he activities for methanold ecomposition remarkably.…”

Section: Introductionmentioning

confidence: 99%

Direct Synthesis of Hydrogen and Dimethoxylmethane from Methanol on Copper/Silica Catalysts with Optimal Cu⁺/Cu⁰ Sites

Wu

¹

,

Li

²

,

Zhao

³

2018

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Hydrogen is an important sustainable resource, and here we report a catalytic route for the direct production of hydrogen (with a purity of 95 %) and dimethoxylmethane (DMM) from supercritical methanol over a Cu/SiO2 catalyst prepared by deposition–precipitation with ammonia (DPA) at 240°C in a one‐pot process. The procedure starts with methanol dehydrogenation to hydrogen and formaldehyde at the interface of the Cu2O⋅SiO2–Cu0 particle mixture, and subsequently, the formaldehyde intermediate condenses with substantial methanol to form DMM in the liquid phase. The Cu0, CuO, and chrysocolla species are inactive for hydrogen generation from methanol, and the intrinsic active species for methanol decomposition is the Cu2O⋅SiO2–Cu0 nanoparticle interface, which is produced from the hydrogen reduction of Cu2Si2O5(OH)2 or from the methanol reduction of Cu−O−Si moieties. A correlation between the structure and activity on reduced Cu/SiO2 (DPA) suggested that only Cu0 was not active, but the combined Cu0 and Cu+ sites with interfaces on SiO2 with an optimal Cu+/Cu0 ratio of 1.56 were highly active for methanol dehydrogenation and subsequent condensation steps. The developed new catalytic system offers a facile and atom‐economical way to generate pure hydrogen (almost CO free) from liquid methanol that can be used in fuel cell and hydrogen‐involved biomass reactions.

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Catalysts for the Formation of Alcohols from Carbon Monoxide and Hydrogen¹: I—Decomposition of Methanol by Catalysts Composed of Copper and Zinc

Cited by 34 publications

References 0 publications

Methanol Synthesis

Methanol Synthesis

Catalysts for the Formation of Alcohols from carbon Monoxide and Hydrogen

Direct Synthesis of Hydrogen and Dimethoxylmethane from Methanol on Copper/Silica Catalysts with Optimal Cu⁺/Cu⁰ Sites

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Catalysts for the Formation of Alcohols from Carbon Monoxide and Hydrogen1: I—Decomposition of Methanol by Catalysts Composed of Copper and Zinc

Cited by 34 publications

References 0 publications

Methanol Synthesis

Methanol Synthesis

Catalysts for the Formation of Alcohols from carbon Monoxide and Hydrogen

Direct Synthesis of Hydrogen and Dimethoxylmethane from Methanol on Copper/Silica Catalysts with Optimal Cu+/Cu0 Sites

Contact Info

Product

Resources

About

Catalysts for the Formation of Alcohols from Carbon Monoxide and Hydrogen¹: I—Decomposition of Methanol by Catalysts Composed of Copper and Zinc

Direct Synthesis of Hydrogen and Dimethoxylmethane from Methanol on Copper/Silica Catalysts with Optimal Cu⁺/Cu⁰ Sites